Composition of matter and method of manufacturing same



I atented Oct. 1 1.940

UNITED STATES PATENT OFFICE.

COMPOSITION OF MATTER AND METHOD OF MANUFACTURING SAME Charles Blair, Jr., Webster Groves, Mm, asslgnor to Petrolite Corporation,

Ltd Wilmington,

Del., a corporation of Delaware No Drawing. Original application December 12, 1 1938, Serial No. 245,230. Divided and this applicationJuly 19, 1939, SerialN o. 285,351

12 Claims. (01. 260 104) time object of my invention is to provide a new n compound or composition of matter, that is particularly adapted for useas a demulsifier in the resolution of petroleum emulsions of the waterin-oil type, but which may have uses in other arts that I have not yet investigated. 3

another object of my invention is to provide a novel method by which said new compound or composition of matter can be produced or manufactured, easily and-economically. The new compound or composition of matter as which constitutes one feature of my present invention, consists oi a certain kind of hydroxylated amino polymeric sub-resinous material of the hind derivable hypothetically by esteriflcation reaction between' (A) a neutral hydroxylated body as containing at least one detergent-forming acid radical; a polyhydric alcohol radical; and at least two hydroxyl radicals; and (B) a substituted amino succinic acid characterized by the fact that at least one amino hydrogen atom has been as replaced by a hydroxy hydrocarbon radical. Needless to ,say, homologues of amino succinic acid" may be considered suitable; for instance, the corresponding amino derivatives of methyl succinic acid, ethyl succinic acid, hexyl succinic an acid, benzyl succinic acid, etc.

,"It is well known that certain monocarboxy organic acids containing approximately eight carbon atoms or more, and not more than 32 carbon lit atoms, are characterized by the fact that they an combine with alkalis to produce soap or soaplike materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula R.COQH. (gerss tain derivatives of detergent-forming acids react with alkali to produce soap or soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergent-forming acids; for instance, instead of fatty acids, one might .employ 50 the chlorinated fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

Included among the various polyhydric alco-' t5 hols which may be employed in the manufacture of the compounds contemplated herein are the following glycerol, diglycerol, trlglycerol, tetraglycerol, various glycols, and polyglycols; or polyhydric ether type materials derived by com--' bination of both glycol and glycerol radicals; or derivatives of, glycerol and polyglycerols with monohydric alcohols; substituted glycerols, such as methyl glycerol, ethyl glycerol, etc.

Among the various glycols are: ethylene glycol, diethylene glycol, triethylene glycol, ethylene propylene diglycoLand various other polyglycols, as well as glycols oi the general formula ilnllalwfil s, in which 12. may represent a number as large as iii. In many instances materials such as ethylene snide, clycide, glycerol chlorhydrin, etc., will act in, the same manner as the corresponding polyhydric alcohol. Such materials are the obvious functional equivalent of the polyhydric alcohols, and may be used if desired, although generally speaking, their cost in contrast with the poly hydric alcohols precludes. their utilization. In other instances there are available certain naturally-occurring combinations of detergent-formill ing acids and polyhydric alcohols which can be employed without further reaction, as, for instance, triricinolein, which constitutes about 85 to 90 percent of ordinarycastor oil.

It is well known that there is available, or that one can readily prepare, substituted succinic acids, or substituted homologues or isologues oi succinic acid, which may be indicated by the following formula:

I R! 'r' n -tx-ooon N-c-cooH w! RI"! I V in which R", R', or R! represents ahydrogen atom or a monovalent hydrocarbon radical, such as an alkyl radical, an alkyl-oxy-alkyl radical, analicyclic radical, an aryl radical, an aralkyl radical, etc., at least one occurrenceot T' represents a hydroxy hydrocarbon radical, such as a hydroxy-alkyl radical, a hydroxyl alicycllc rad ical, an aryl hydroxy alkyl radical, a hydroxy alkyl radical interrupted at least once by an oxy gen atom, etc, and the other occurrence of T ;may be the same, or may be a hydrogen atom or a hydrocarbon radical, such as an alkyl radical,

an alkyl radical interrupted at least once by an oxygen atom, an alicyclic radical, an aryl substituted alkyl radical, etc., but does not represent an aryl radical. a As has been previously indicated, one of the reactants employed is a derivativeof a polyhydric Examples include mono-olein,

alcohol and a detergent-forming acid. Obviously, the two or more chemical compounds which produce such reactant may be used separately instead of the final compound itself. However, for the sake of clarity, hydroxylated polyhydric alcohol detergent-forming acid bodies, that is, materials of the kind previously referred to, will be described in detail. Such esters are considered as being multi-active, because such compounds must contain at least two alcoholic hydroxyl radicals, and can combine with a dibasic carboxy acid, such as asubstituted amino succinic. acid at at least two different points of reaction.

One class of multi-reactive materials includes triricinolein, trihydroxystearin, ethylene glycol diricinoleate, ethylene glycol dihydroxy stearate, ethylene glycol di-oxynaphthenate, ethylene gly-' col di-oxyabietate, etc. A second class of multireactive compounds consists of derivatives, in which there is no alcoholic hydroxyl radical attached to the detergent-forming acid radical, but in which there are at least two hydroxyls attached to the parent polyhydric alcohol radicals. mono-stearin, mono-abietin, mono-naphthenin, and similar derivatives derived from the polyglycerols, such as diglycerol, triglycerol, etc.

A' third class of materials includes those in which there is at least one alcoholic hydroxyl radical attached to a detergent-forming acid radical, and at least one hydroxyl radical attached to the parent polyhydric alcohol residue. This class includes materials, such as monoricinolein, diricinolein, monohydroxystearin, dihydroxystearin, monohydroxy abietin, mono-oxynaphthenin, etc. including derivatives obtained from the glycols, polyglycols, polyglycerols, etc.

Simple consideration indicates that one might have various kinds of mixed esters; for instance, one mole of glycerol might be esterifled with one mole of ricinoieic acid and one mole of oleic acid, or one mole of abietic acid and one mole of naphthenic acid. Similarly, digiycerol might be esterifled with one mole of stearic acid and one mole of oleic acid, or with one mole of palmitic acid and one mole of abietic acid, or with one mole of abietic acid and one mole of naphthenic acid. A large number of similar combinations immediately suggest themselves. The multi-reactive esters of the kind referred to may be indicated by the following formula:

(oar/.000).

- ber of theclass. consisting of hydrocarbon radicals once by an oxygen atom; 11. represents 0, 1, 2, 3, 0r 6; n represents 0, 1, 2, 3, or 4; 'm represeats 0, 1, 2, 3, 4, or 5, with the proviso that n+n' must be at least one and not over 6, and

that m-i-n must be at least'2. It is to be noted that 0H.R'.COO represents a hydroxylated de-, tergent-forming acid and is intended to include the particular species in which" more than one hydroxyl is included, such as dihydroiwstearic acid, etc. Dihydroxystearic acid is the obvious equivalent of ricinoleic acid or hydroxystearic acid, as has been previously pointed out, and is to be so construed, of course, in all subsequent formulas and in the claims.

-If, for the sake of convenience, hydroxylated substituted amino acids of the kind previously described are indicated by the formula;

HCOO.T.COOH

in which T represents that part or radical of certain substituted succinic acids or the like other than the carboxylic radicals, and which acids have been described completely in the first formula appearing in the present specification then the simplest esteriflcation reaction product derived from multi-reactive esters of the kind described above may be indicated by the following If, however, a third molecule of water would be eliminated from the same two monomers, it would mean two monomers have joined to produce a dimer or a polymer. As far as the present invention -is concerned, it is limited solely to polymeric forms, 1. e., dimers and higher forms, which are described in greater detail, subsequently, except to the extent that certain'hereto attached claims contemplate the crude material of final reaction, which may, and undoubtedly does, contain at least a limited minor portion of monomers.

It has been previously pointed out that a material such as tetraglycerol may be employed. Tetraglycerol is characterized by six alcoholic hydroxyl radicals. Therefore, theoretically, at least, one mole of tetraglycerol could be united with six moles of ricinoleic acid; andone mole of the ester so formed could be united with six moles of a dicarboxy acid. Similarly, any dicarboxy acid could combine with at least two moles of a compound containing a free hydroxyl radical, and for these reasons it is obvious that the polymeric materials contemplated herein are not limited to those obtained as a result of equi-molar reactions, but that the formula above described may be advantageously rewritten as follows:

oaancoo I]: D o11)..] [H.COO.T.CO0H] 141110 (ii-.000);

For the moment, no attempt will be made to define x, y, and 111. until consideration 'is-given to their probable order of magnitude. In view of what has been stated by Kienle, Industrial 8: Engineering Chemistry, volume 22, No. 6, p. 590, and elaborated by subsequent investigators, (see Ellis, Chemistry of Synthetic Resins, volume II, 1935, particularly chapters 41-49, inclusive), it is probable t at :0 cannot reasonably represent a number gre ter than 30. It has been previously pointed out that theoretically, at least, 1 might. become 6 .times 1:; and therefore, y is limited to 180.

Theoretically, at least, m might also be as much till.

bill

' aminolysis reaction takes place.

a,s1e,s1o as 360, since one molecule of water could be formed for each carboxyl hydrogen atom present. with these facts in mind in the above formula, :1: willbe designated as representing a numeral greater than one and not over 30; y will be represented as designating a numeralgreater than one after discussed, yet it does not represent a suit able method of manufacture, i. e., esteriflcation of the multi-reactive ester with a suitable amino succinic acid, for the following reasons:

'(a) It contemplates themse of an amino. acid which may act in the manner of an inner salt. comparable, perhaps, to amino benzoic acid, and which would not be readily adapted to a reaction of the kind contemplated;

(b) Furthermore, since the particular amino acid employed is characterized by the presence of an alcoholichydroxyl'radical, lactone-like materials might be produced or polymerization might take place between various molecules of the hydroxyamino acid;

(c), In addition, since some of the amino acids would represent secondary amines, i. e., still have available an amino hydrogen atom, it is obvious that acylation might take place, which would be undesirable.

For these reasons, and for other reasons which are obvious, I have found it necessary to produce such sub-resinous compounds herein conte'm platedby a new and novel method.

In-employing my particular method for the manufacture of su'chsub-reslnous compounds of the kind described, I resort to theuse of maleic anhydrlde or its obvious equivalent, such as maleic acid, fumaric acid, and in certain instances, half salts and half esters, such as sodium acid maleate, ethyl acid maleate, etc. It is well .lrnown that if esters of maleic acid are treated with primary or secondary amines, 'a saturation- This reaction may be-indicated in its simplest aspect by reaction between ammonia and dioctyl maleate, indicated'in the following manner:

H H O instead of octyl alcohol, one employed ethylene glycol mono-cleats, that is, a compound containing a polyhydric alcohol residue and also a detergent-formlngacid residue, it would be obvious that the resultant product would be comparable to the materials previously described, except that such a product would represent a monomer.

It is at once obvious that a simple modification of such procedure will result in producing compounds of the type desired. For instance, if mono-olein or diricinolein. or any multi-active ester or reactant of the kind previously described in great detail above, is treated with maleic anhydride, a maleyl halide, or maleic acid or fumaric acid in the conventional manner to produce polymeric or sub-resinous materials, then the product so obtained, provided it is neutral or rendered neutral by any suitable means, i. e., neutralization with sodium hydroxide, potassium hydroxide, ammonium hydroxide, any tertiary porated therein the non-functional variations brought about by neutralizing any carboxylic hydrogen atom before the saturatiomaminolysis reaction is involved. It is necessary to eliminate an acidichydrogen atom contributed by an unneutralizsd carboxyl prior to the saturation-aminqlysis reaction, because it would produce either one of a number of undesirable reactions. such as (a) waste the hydroxyamine employed; (b)

unite, by an esteriflcation reacti n with the hydroxy radical of-the amine, which is undesirable: (c) produce. acylation with the hydroxyamine, if an amino hydrogen atom is present, etc.

In view of what has been said, it is obvious that the previous formula can be rewritten in the following manner:

in which MQH represents a suitable reactant for removing a carboxylic hydrogen atom, such as alkali hydroxide, a monohydric or polyhydric alcohol, or a tertiary amine, or the amine used for the saturation-aminolysis reaction. Examination reveals that 2 should in no instance be greater than /1, y; and therefore, a is momentarily indicated as being a number which varies from 0 to 90. At least' one occurrence of 'I", as previously indicated, represents a hydroxylated hydrocarbon radical of the type T"'(OH)m", in which T' indicates a hydrocarbon radical; m lndb cates a small whole number not greater than 10;

and the other occurrence of T represents the same or a. hydrogen atom or a hydrocarbon radical of the kind previously described. I

It may be well at this point to indicate the various suitable amines which may be employed in the, saturation-aminolysis reaction. Diethanolamine or monoethanolamine might be employed. Cyclohexylolamin or dicycl'ohexylob amine could be employed. Similarly, if one had available aralkylamclnes in which a hydrogen atom in the alkyl residuehad been replaced by a hydroxyl radical, then such aryl alkylolamine would likewise be suitable. If the alkylolamines above described or their equivalents be considered as derivatives of glycols and hypothetically obtained by reacting the glycol chlorhydrin with ammonia, then similarly, it is obvious that various other amines, such as monoglycerylamine,

diglycerylamine, etc., could be employed as well A as. amines obtained from ether alcohols, such as polyglycols or polyglycerols.

In the utilization of secondary amines, it is not necessary that both.substituents for the amino hydrogen atoms be hydroxylated in character; for instance, ethyl ethanolamine, or ethyl propanolamine, or oyclohexyl ethylamine, or amyl glyceryl amine, and the like, may be employed. Compounds of the kind which comprise an integral part of the present invention are characterized by the presence-of at least one hydroxy hydrocarbon radical replacing an amino hydrogen atom in the amino succinic acid radical or. residue. The expression amino hydrocarbon includes amino alkyl-oxy-alkyl residues, as well as those compounds in which the carbon atom chain is not interrupted by an oxygen atom. In-

cidentally, it has been found that the ether linkage of the type exemplified by morpholine is considered the equivalent of a hydroxy radical or grouping, and thus morpholine, although in essence a cyclic oxy-hydrocarbon amine, is considered as being a hydroxy hydrocarbon amine for the purpose of the reactions herein contemplated.

Other suitable amines which may be employed are the following: methyl ethanolamine, propanolamine, dipropanolarnine, oyclohexyl ethanolamine, oyclohexyl propanolamine, benzyl ethanolamine, benzyl propanolamine, pentanolamine, hexanolamine, octyl ethanolamine, octadecyl ethanolamine, cyclohexanol ethanolamine, and polyethylene amines, such as the following:

If one refers to'the last formula previously employed to indicate the composition of the polybasic compounds herein contemplated, it is obvious that, the amino nitrogen is still, basic in character, and therefore, can be neutralized'in the conventional manner with any suitable acid, if desired, such as hydrochloric acid, acetic acid, sulfuric acid, oleic acid, naphthenic' acid, abietic acid, etc. Naturally, when such amine comes in contact with water, it combines to produce a substituted ammonium base. It is intended that all reference herein and in the hereto-appended, claims, to the composition of matter contemplated, shall include the. neutralized or basic form of material (combiiiation with water), as well as the amine form. In order to avoid further complexity of formula, such obvious modifications will be ignored in designating the structure. What is said hereinafter as to the solubility of these compounds refers not only to the amines, but also to the salts and the reaction product obtained with wateryto wit, the base.

An examination of the last formula above employed to indicate the polymeric products which constitute a. feature ofv the present invention, reveals that the formula can-be simplified and still esterification;

edcompounds. Itis obvious that all the acidic hy-- drogen atoms of the substituted amino-succinic acid radical are removed by esterification, or secondary neutralization, as described. Therefore, in the final product the amino-succinic acid radical can be suitably indicated in the form of an oxy-acyl radical or OOC.T.COO. Bearing in mind that the multi-active constituent previously referred to must lose at least two hydroxyl radicals in order to form a polymeric compound (but may lose more than two), it is obvious that the last formula for the polymer product previously referred to may be rewritten as follows:

(a'ooon D(OH),] [000.1000] [z] (R.Co) z y irzhfi-n-pf in which RCOO represents the oxy-acyl acid radical obtained by dehydroxylation of a hydroxy detergent-forming acid; RCOO represents the acid radical or oxy-acyl radical of a non- .hydroxy detergent-forming acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals, in which the carbon atom chain is interrupted at least once by an oxygen atom; T represents the hydroxy hydrocarbon substituted amino succinic acid radical, and Z represents an acidic hydrogen atom substituent; n represents 0, 1, 2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or 4; p represents 0, 1, 2, 3 or 4; m-represents the number of hydroxyl radicals directly attached to D prior to i a: has the same significance as previously, to wit, a number greater than 1 and not over 30; g has the same significance as previously, to wit; greater than 1 and not over 180; and the ratio of m to y is within the limits of 1 to 6 and 2'to 1, respectively, and as previously stated, n+n' must equal at least-one.

Possibly the above formula does recognize insignificant minor variations which are immaterial for practical purposes; For instance, in a polymer, it is possible that the end nuclei derived from a multi-reactive reactant are characterized by the fact that a minimum of two hydroxyls are not removed and only one is removed, although this is not true if a cyclic structure results. It is understood, of course, that the above formula contemplates that ,the terminal 'nuclei derived The products hereincontemplated are referred to as soluble polymeric sub-resinous materials. The products are referred to as soluble, because within the order of magnitude in which they may be used in breaking oil field emulsions, to wit, 1 to 10,000 or 1 to 30,000, or thereabouts, the products in one or more of their 'various forms are soluble in crude oil or in water, or inboth. The word soluble is used to indicate molecular solubility of colloidal solubility. 'These materials are referred to as being sub-resinous, because in view of the molecular size, as indicated by the values for a: and y, it appears that such materials do. not reach a true resinous stage. This is indicated,

lit.

we to give resins.

ferred to. True resins do not exhibit such solubility. It is not intended to infer that such multi-active reactants of the kind described could necessarily be polymerized with a dibasic carboxy Many of such reactants, and perhaps all of them, if heated indefinitely prior to me saturation-aminolysis reaction, would not produce a. true resin, for reasons which are well understood, and which have been stated by Kienle, previously referred to. In any event, the final product can beexamined by the usual cryoscopic methods, or other suitable methods, and the molecular weight so determined considered as being the molecular weight of the product.

The materials employed should have a molecular weight of less than 100,090; and as far as I able to determine, those coming within thel molecular weight range of approximately 2,000, or- 29990 appear to be most desirable. Excessive molecular weights indicate that lower temperuture of reaction or smaller time of reaction should be employed. It the product exhibits too low a molecular weight, the indicated requirements are for higher temperature or longer time of reaction, or both. Reference to reaction means reaction, of course, prior to aminolysis.

The presence of an excessive number of hydroxyl radicals makes for higher molecular weights.

lit is obvious that any method of manufacture,

and particularly the method which I employ, may result in the formation of some limited minor amount of monomeric compounds, as well as poleric sub-resinous compounds. As far as I know, there is no objection to the presence of a minor amount of monomeric material; and in fact, such monomeric materials may be helpful in promoting the solubility of the polymeric materials in oil or water. In order that it may be understood that I particularly contemplate the preferred product obtained by the specified, method of manufacture outlined, which includes a certain amount of monomeric materials, and perhaps other valuable byproducts, it has been deemed desirable to direct claims both toa composition of matter, as indicated by the structural formula above, andalso a composition of matter produced by the particular method herein described, in order to include the admixture with these monomeric materials.

Attention isnow directed to the actual method of manufacture which ,I'employ. For the sake oi convenience, hereafter the expression "alkyl will be used in its broadest sense to include an nlhyl-oxy-allryl radical, i. e., an alkyl radical in which the carbon atom chain has been interoil. I prefer to employ monoricinolein or diricinolein, or the equivalent product derived from blown castor oil by treatment with an excess of glycerol in the usual manner. A suitable composition of matter which is particularly adapted for use as a .demulsifierin the resolution of petroleum emulsions of the water-in-oil type is premole of maleic anhydride for approximately three hours at 120 C. with constant stirring; and then for approximately two hours at about 190 C., with further stirring. The product is allowed to cool and is tested for, absence of acidity. If it 5 should show any acidity, due to the presence of an unesterified carboxyl radical, a small amount of glycerol is added and the mass reesterified for approximately 30 minutes to an hour until the product is neutral. It is then allowed to cool to room temperature, approximately 25 C., or thereabouts, and cautiously treated with one mole of ethanolamine. The saturation-aminolysis reaction, previously referred to, takes place 1 Obviously, where an ester is produced with an excess of hydroxyl radicals, one could, if desired, add a certain amount of half ester of half salt derived from malelc acid, such as sodium hydrogen maleate, ethyl hydrogen maleate, etc., to complete or finish off the esterification reaction. Similarly, as has been suggested previously, instead of employing the multi-active reactant, one could employ the constituents or reactants and 85 produce the same. For instance, instead of employing monoolein, one could employ a suitable mixture of glycerine and oleic acid, or, if desired, one could react the maleic anhydride or its equivalent with the selected polyhydrio alcohol, such as glycerol, and then esterify such product with the selected detergent-forming acid, such as oleic acid, prior to aminolysis. However, it is found to be most satisfactory by far to employ the pro'te'dure described, in preparing the preferred reagent. If such procedure is followed, then one readily obtains a material which exhibits the desired solubility and the desired molecular weight to place it clearly within the polymeric subresinous range previously specified. 50 As to the manufacture of polymeric sub-resinous materials from maleic anhydride and the like and various multi-active reactants of the kind previously des ribed, attention is directed to the previous refer ces, to Kienle, Ellis, and also to the following seven United States Patents No. 1,976,602, Oct. 9, 1934, and No.-1,977,048, Oct. 16, 1934, Melvin De' Groote et al.; Nos. 1,977,089 and 1,977,146, Oct. 16, 1934, No. 1,978,227, Oct. 23,

1934, No. 1,979,347, Nov. 6, 1934, and No. 2,000,717, May 7, 1935, C. H. M. Roberts.

These above cited patents are referred to, not

because they teach the use of malelc acid or maleic anhydride exclusively, but because they teach the manufacture of various materials from polybasic acids; and'a person skilled in the art can readily make the necessary changes so as to employ malelc acid or maleic anhydride, instead of phthalic acid, oxalic acid, and the like, and obtain polymeric sub-resinous materials of the kind herein contemplated.

Conventional demulslfying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum-hydrocarbons, such as 76 gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleurn, etc., may be employed as diiuents. Similarly, the new material or composition of matter herein described may be admixed with one or more of .the solvents customarily used in connection with conventional demulsifying agents. Moreover, said new material or composition of matter may be used'alone or in admixture with other suitable well known classes of demulsifying agents, such as demulsifying agents of the modified fatty acid type; the petroleum sulfonate type, the alkylated sulfa-aromatic type, etc.

It is well known that conventional demulsifying agents may be used in water-soluble form, or in an oil soluble form, or in a form exhibiting both 011 and water solubility. It has been previously pointed out that the new material or composition of matter that constitutes my present invention is characterized by the fact that it is soluble within the limits of use, as previously indicated.

I desire to point out that the superiority of my new compound or composition of matter as a demulsifler for crude oil emulsions, is based upon its ability to treat certain emulsions more ad- 'vantageously and at a somewhat lower cost than is possible with other available demulsiflers, or conventional mixtures thereof. It is believed that the new material orcomposition of matter herein described will-find comparatively limited application as a demulsifler, so far as the majority of oil field emulsions are concerned; but I have found that said material has commercial value, as it will economically break or resolve oil field emulsions in anumber of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In using my new material or composition of matter to resolve cut oil, roily oil, emulsified oil," etc., a treating agent or demulsifying agent consisting of or comprising said new material is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways or by any-of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

Having thus described my invention, what I claiiixsi as new and desire to secure by Letters Patent 1. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight or less than 100,000, and char acterized by the formula type:

in which R COO represents the acid or oxy-acyl radical obtained by dehydroxylation or a hydroxy detergent-forming acid; R.COO represents the.

an oxygen atom; drocarbon substituted amino succinic acid radicarbon atom chain is interrupted at least once by an oxygen atom; T represents the hydroxy hydrocarbon substituted amino succinic acid radical, and Z represents an acidic hydrogen atom substituent; n represents 0, 1, 2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or 4, with the proviso that n+n' must equal at least 1; 1) represents 0, 1, 2, 3, or 4; m represents the number of hydroxyl radicals directly attached to D prior to esteriflcation; 1: represents a number greater than 1 and not over 30; y represents a number greater than 1 and not over and the ratio of :c to y is within the limits of l to 6 and 2 to 1, respectively.

2. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight within the range of 2,000 to 25,000, andcharacterized'by the formula type:

in which R'COO represents the acid or oxy-acyl radical obtained by dehydroxylation of a hydroxy detergent-forming acid; acid or oxy-acyl radical of a non-hydroxy detergent-forming acid; D represents'a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals in whic the carbon atom chain is interrupted at least once by T represents the hydroxy hycal, and Z represents an acidic hydrogen atom substituent; n represents 0, .1, 2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or

n+n must equal at least 1; 11 represents 0, 1, 2,

R.COO represents the v 4, with the proviso that 3, or 4; m represents the number of hydroxyl radicals directly attached to D prior to esterification; n: represents a number greater than 1 and not over 30; 11/ represents a number greater than 1 and not over 180; and the ratio of a: to y is within the limits of 1 to 6 and 2 to 1, respectively.

3. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight within the range .of 2,000 to 25,000, and characterized by the formula type:

radical obtained by dehydroxylation of a hydroxyfatty acid, H.000 represents the acid or o acyl radical of a non-hydroxy fatty acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals in which the carbon atom chain is interrupted at least once by an oxygen atom; T represents the hydroxy hydrocarbon substituted amino sulionic acid radical, and Z represents an acidic hydrogen atom substituent; n represents 0, 1,2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or 4, with the proviso that n-i-n' must equal at least 1; :2 represents 0, 1, 2, 3, or 4; m represents the num-. ber of hydroxyl radicals directly attached to D prior .to esteriflcation; 1 represents a number greater than 1 and not over 30; 11 represents a number greater than 1 and not over 180; and the ratio of a: to 11 is within the limits of 1 to 6, and 2 to 1, respectively.

4. A composition oi matter, comprising a soluble polymeric sub-resinous product having a succinic acid radical, and Z represents an acidic molecular weight within the range of 2,000to 25,000, and characterized by the formula type:

rupted at least once by an oxygen atom; T repre-- sents the hydroxy hydrocarbon substituted amino hydrogen atom substituent; n represents 0, 1, 2, 3,

l, 5, or 6; n represents 0, 1, 2, 3 or 4, with the proviso that n+n' must equal at least 1; p represents 0, 1, 2, 3, or 4; m represents the number of hydroiryl radicals directly attached to D prior to esteriflcation :1: represents a number greater than 1 and not over 30; 1 represents a number greater than 1 and not over 180'; and the ratio of a: to y is within the limits of 1 to 6 and 2 to 1, respectively;

and additionally characterized by the tact that said composition of matter is derived solely from castor oil, glycerol, maleic anhydride, and an ethanolamine containing at least one amino hydrogen atom. t

5. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight of less than 100,000,and obtained by subjecting a neutral polymeric subresinous product derived from maleic anhydride and a multi-active reactant of the formula type:

, tomncooo mom.

in which RG00 represents the acid or oxy-acyl radical of a monobasic carboxy detergentformlng acid; OH.R'.COO represents the samederivedfrom a hydroxylated monobasic carboxy detergent-forming acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals in which the carbon atom chain is interrupted at least once by an oxygen atom; n represents 0, l, 2, 3, 4i, 5, or 6; n represents 0, 1, 2, 3, or 4; m represents 0, 1, 2; 3, 4, or 5, with the proviso that'n+n' must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical, as a substituent for an amino hydrogen atom.

6. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight within the range of 2;000 to 25,000, and characterized by subjecting a neutral polymeric sub-resinous product derived from derived from a hydroxylated monobasic car-boxy detergent-forming acid; D represents amember of theclass. consisting of hydrocarbon radicals and ether-type oxyhydrocarbcnradicals in which the carbon atom chain is interrupted at least once by ah oxygen atom; n represents 0, 1, 2, 3, 4, 5, or 6'; n represents 0, 1,. 2, 3, or 4; m represents 0, 1, 2, 3, 4, or 5, with the proviso that n+n must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence oi. at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom.

7. A composition of matter, comprising a soluble polymeric sub-resinous product having a molecular weight within the range of 2,000 to 25,000, and obtained by subjecting a neutral polymeric sub-resinous product derived from maleic anhydride and a multi-active reactant oi the formula type:

. in which RG00 represents the acid or oxy-a'cyl with the proviso that n+n must be at least one andnot over 6 and that m+n mustbe at least 2;

to an amlnolysis reaction with an amine, said amine being characterized by the presence .of at least one amino hydrogen atom and by the pres-Q in which RCOO represents the acid or oxy-acyl radical of a fatty acid; OH.R'.COO represents the same, derived from a hydroxylated fatty acid; D represents amember of the class consisting of hydrocarbon radicals andether-type oxyhydrocarbon radlcals'in which the carbon atom chain is interrupted at least once by an oxygen atom; n represents 0, l, 2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or 4; m represents 0, 1, 2, 3,

4, or 5, with the proviso that n+n' must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence. of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom; and additionally characterizedby the fact that said composition of matter is derived solely from castor oil, glycerol, maleic anhydride, and an ethanolamine containing at t least one amino hydrogen atom.

9. A method for manufacturing soluble polymeric sub-resinous products having a molecular weight of .less than 100,000, which comprises subjecting a neutral polymeric sub-resinous product derived by esterifying maleic anhydride with a multi-active reactant of the formula type:

in which R.COO represents the acid or oxyacyl radical of a monobasic carboxy detergentforming acid; OH.R'.C0O represents the same derived from a hydroxylated monobasic carboxy detergent-forming acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals in which the carbon atom chain is interrupted at least once by an oxygen atom; 11 represents 0, 1, 2, 3,-

4, 5, or 6; n represents 0, 1, 2, 3, .or 4; m represents 0, 1, 2, 3, 4, or 5; with the proviso that n-i-n must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom.

10. A method for manufacturing soluble po1ymeric sub-resinous products having a molecular.

weight within the range of 2,000 to 25,000,'which comprises subjecting a neutral polymeric subresinous product derived by esterifying maleic anhydride with a multi-active reactant of the formula type:

olminooo),a

I m m. 3.000): in which R.COO represents the acid or oxy-acyl radical of a monobasic carboxy detergent-forming acid; OH.R'.COO represents the same, de-- rived from a hydroxylated monobasic carboxy detergent-forming acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrccarbon radicals in which the carbon atom chain is interrupted at least once by an oxygen atom; n represents 0, 1,

2, 3, '4, 5, or 6; n represents 0, 1, 2, 3, or 4; m represents 0, 1, 2, 3, 4, or 5, with the proviso that n+n' must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom.

11. A method for manufacturing soluble polymeric sub-resinous products having a molecular weight within the range of 2,000 to 25,000, which comprises subjecting a neutral polymeric subresinous product derived by esterifying maleic anhydride with a multi-active reactant of the formula type:

(OH.R.CO0)

(R.COO),.'

in which R.COO represents the acid or oxy-acyl radical of a fatty acid; OH.R.COO represents the same, derived from a hydroxylated fatty acid; D represents a member of the class consisting of hydrocarbon radicals and ether-type oxyhydrocarbon radicals in which the carbon atom chain is interrupted at least once by an oxygen atom; n represents 0, 1, 2, 3, 4, 5, or 6; n represents 0, 1, 2, 3, or 4; m represents 0, 1, 2, 3, 4, or 5, with the proviso that n+n' must be at least one and not over 6 and that m+n must be at least 2; to an aminolysis reaction with an amine, said amine being characterized by the presence of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom.

12. A method for manufacturing soluble polymeric sub-resinous products having a molecular weight within the range of 2,000 to 25,000, which comprises subjecting a neutral polymeric subresirrous product derived by esterifying maleic anhydride with a multi-active reactant of the formula type:

in which R.COO represents the acid or oxy-acyl 0, f, 2, 3, or 4'; m represents 0, 1, 2, 3, 4, or 5, I

with the proviso that n+n' must be at least one and not over 6 and that m+n must be at least 2; to an aminolysls reaction with an amine, said amine being characterized by the presence of at least one amino hydrogen atom and by the presence of at least one hydroxy hydrocarbon radical as a substituent for an amino hydrogen atom; said method being additionally characterized by emp oying as sole raw materials, castor oil, glycerol, In leic anhydride, and an ethanolamine containing at least one amino hydrogen atom, 1 CHARLES M. BLAIR, JR. 

